Process for the polymerization of ethylene



Oct. 15, 1963 G. w. HOOKER PRocEss FOR THE POLYMERIZATION oF ETHYLENE Filed June e, 1955 2 Sheets-Sheet l L v KV T R R L a m IW N m O l fNvI w WM .o n nl. n l? n., P w. 5 www Q wu m Fs o um. Y Um 1. WA B D x a N x .5. j n n 5 H u m u L 4f@ m 1w n 1 w. x on 5W G n M fw m E L l Ilm o o @www .Wlod X .flung I (HFZNNKRHD Tod x krumm m m m o (il l" Oct. 15, 1963 G. wfHooKER A PRocEss FOR wpommalzmon oF ETHYLENE Filed June e', 1955 2 Sheets-Sheet 2 Inn-@EAL @EIGHT Drs-mxu'rxou Cueva ExAmPLE. I.

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INVHV TOR. 650265 M Hooxa United States Patent O 3,167,233 PRCESS FR 'HE PLYPMRIZATHN @E E'ir @ENE George W. Hooker, New Brighton, Pa., assigner to Hoppers Company, lne., a corporation oi Beiaware Fiied .Enne (i, 1955, Ser. No. 513,313. li Claims. (Cl. 26d-94.9)

This application is concerned with a process for the polymerization of ethylene. More particularly the application is concerned with a process for the polymerization of ethylene in the presence of a catalyst which is a mixture of (A) and (B) in which (A) has the general formula RRAIX, in which R is a member selected from the group consisting of hydrogen, alkyl radicals and aryl radicals, R is a member selected from the group consisting of hydrogen, alkyl radicals, and aryl radicals, and in which X is a member selected from 4the group consisting of hydrogen, alkyl, halogen a-toms, alky-loxy radicals, aryloxy radicals, secondary amino radicals, secondary acid amide radicals, mercapto radicals, thiophenyl radicals, radicals of carboxylic acids and radicals of sulfonic acids7 and in which (B) is a compound of a metal selected from the group consisting of metals of group IV-B, V-B, and 'VI-B of the periodic system including thorium and uranium at temperatures under the decomposition temperature or" the particular catalyst, `that is in the order rof 100 C. and at pressures of less than 100 atmospheres. Suitably these catalysts are slurried or dissolved in an ine-rt solvent such as, for example, heptane, hexane, pentane, cyclohexane, tetrahydronaphthalene, decahydronaphthalene, benzene, Xylene, o-dichlorobenzene, chlorinated naphthalene, dibutylether, an-d the like.

It is known, as taught .in Ziegler Belgian Patent 533,- 362, issued May 16, 1955, to the polymerize ethylene in the presence of the aforementioned catalysts. Conveniently this is accomplished by preparing a mixture of the catalyst and a liquid inert solvent and introducing ethylene below the liquid level while stirring until a slunry of polyethylene is obtained.

It has now been discovered yas a feature of this invention that the molecular weight distribution of polyethylene produced by contacting ethylene with an aforementioned catalyst in an inert solvent can be ydesirably altered by running the polymerization in a continuous manner as hereinafter described, Thus the present invention broadly embraces a process for the polymerization of ethylene comprising continuously and simultaneously adding to a reaction zone ethylene, a catalyst and an inert solvent in liquid form, withdrawing polymer slurry from said zone and separating the polyethylene therefrom. Advantageously the slurry is withdrawn at such a rate as to maintain the amount of constituents in the reaction zone substantially constant. Advantageously it includes maintaining said reaction zone constituents in the temperature range of from about 50 C. to about 85 C. and in which said catalyst is as aforedescribed.

In another embodiment the invention embraces a process for the polymerization of ethylene comprising continuously and simultaneously adding to a reaction zone ethylene, a solution of catalyst component (A) in an inert solvent and a solution of catalyst component (B) in inert solvent while withdrawing polymer slurry from said zone at a rate to maintain the amount of constituents in said reaction zone substantially constant, and in which the catalyst components (A) and (B) are as aforedescribed.

As mentioned above polymerizing ethylene in accordance with ythe present invention enables one to obtain polyethylene in which the molecular Weight distribution varies only over a limited range vas compared to the distribution of molecular weights obtained by operating as ''ZBS Patented Get. i5, 1853 ICC heretofore known by a batch procedure. These difierences are illustrated by FIGURES l and 2 which are the ldifferential weight distribution curves for the polyethylencs of Examples '1 and 2. The slopes dy/dx from the integral distribution curves are plotted against molecular Weight. The slopes are obtained from FIGURES 3 and 4 which are the integral distribution curve for polyethylenes produced by Examples l and 2. In these FIGURES 3 and 4 the cumulative percent polymer is plotted as the abscissa and molecular Weight as -the ordinate. It will be noted that the differential weight distribution curve (FIG- URE 2) of the polyethylene of Example 2 has two peaks. That is, there are two sizable fractions of the polymer having markedly diiering molecular weights. On the other hand the differential weight distribution curve (FIGURE l) for the polyethylene of Example l shows only a single peak. 'Iihat is, the major fraction of this polyethylene has molecular weights varying within a limited range as compared to the polyethylene of Example 2.

The continuous addition of the various components required for Ithe reaction to a reaction zone can be accomplished in a variety of ways. For example, the catalyst components (A) and (B) can be admixerd with the inert solvent and this mixture added to the reaction zone while simultaneously and continuously, ethylene is added and polymer slurry withdrawn. Alternatively there can be prepared separate solutions or mix-tures of catalyst components (A) and (B) in the inert solvent and these can be added as separate streams as aforedescribed to the reaction zone. In another variation there can be utilized in place of fresh inert solvent quantities of the liquid residue obtained by separating polyethylene from the polymer slurry. This liquid residue and make-up quantities of inert solvent can be utilized to prepare catalyst mixes which are ythen introduced to the reaction zone as astoredescribed. Further, this liquid residue can be recycled to the reaction zone while there is added make-up quantities of catalyst and inert solvent mixture or make-up quantities of catalyst components (A) and (B) and inert solvent in separate streams as aforedescribed. FIhe advantages obtained by such recycle procedures are de scribed and claimed in the copending application tof lohn W. Martin, Ir., Serial No. 513,567, tiled concurrently herewith (now abandoned).

The desirable results are obtained with -any of these variations. It is further to be realized that, while the word continuously has been used in describing the manner of addition of the various components, this addition can be accomplished advantageous-ly by incremental additions of the components, such as yfor example, that which is accompanied by the use of a proportioning pump. Such pump, of course, does not deliver on the intake stroke but adds material to the reaction zone in a substantially continuous, but incremental fashion. This is contemplated by the present invention.

Similarly, while it is desirable to withdraw continuously from the reaction zone the polymer `slurry this too can be accomplished in an incremental fashion; that is, for example the liquid level can be allowed to rise during a period when polymer is not being withdrawn. Thereafter polymer slurry can be withdrawn at a rate greater than that at which the catalyst, inert solvent and ethylene are being added to effect a lowering of Ithe liquid level in the reaction zone to a point below the normal liquid level. Preferably, the Variations in the liquid level should not effect a change in the 'volume of reaction zone constituents in excess of about l0 percent from the volume of constituents present when the normal liquid level obtains. In comparison, the continuous and simultaneous introduction of the catalyst, inert solvent and ethylene is of markedly more importance to a realization of the advantages of this invention, than the withdrawal of the polymer slurry.

Thus it Will be seen that the present invention provides a'means of producing polyethylene having minimum moecular weight distribution.

As used herein the terms parts and percent mean parts and percent by weight unless otherwise specied.

EXAMPLE 1 To a suitable glass-lined reaction vessel equipped with a stirrer and a reux condenser there is added a mixture of 1780 parts of dry heptane, 3.42 parts of diethylaluminum chloride and 5.61 parts titanium tetrachloride. Ethylene at the rate of about 50 parts per hour is added below the liquid level while the contents are stirred and in approximately 41/2 hours there is obtained a sluiry of polyethylene. There is then ycommenced the simultaneous and continuous addition of the above described catalystheptane mixture at `the rate of approximately 400 parts per hour and the addition of ethylene at the above rate is continued.

There is also commenced at this time the withdrawal of polymer slurry at the rate of approximately 450 parts per hour. The temperature of the reaction zone is maintained at about 52-5 3 C.

This run is continued and during the eighth to tenth hours of simultaneous and continuous addition of reactants and withdrawal of slurry of the polyethylene separated from the `slurry is sampled and its average molecular weight determined to be 42,000. This sample is representative of the polyethylene produced by the continuous method of operating during the period of simultaneous and continuous addition of catalyst-inert solvent mixture ethylene.

Data for the integral distribution curve (FIGURE 3) for this sample is obtained as follows:

A film is prepared by dipping a foil into a solution of 2 grams polyethylene sample in 100 mm. xylene. The ilm is allowed to dry. There is prepared a 40/ 60 volume ratio mixture of toluene and normal butanol which is heated to 100 C. in an oil bath. Then the aluminum foil containing the polyethylene -lm is placed in a fractionator maintained at 100 C. There is added to the tractionator 100 m-m. of the toluene-normal butanol mixture and the system allowed to stand for minutes during which time the fractionator is agitated slightly to give a swirling motion -to the liquid contents. The solution is removed rom the fractionator and evaporated -to dryness and the residue weighed. The procedure is then repeated with the varying volume ratios of toluene and normal butanol listed in Table 1 under the heading Toluene-n- Butanol, Volume Ratio. There are observed the data set -forth in the column heated Percentage Polymer, Based on Total.

Table 1 Toluene-n- Percentage Cumulative Molecular Fraction butanol, polymer percentage Weight,1

volume based on polymer Mn ratio total 1 1.141X10a M1104.

Molecular Weights are observed by ldetermination of the inherent viscosities of the lfractions in decalin at 135 Table 2 y; y2 dy Molecular dx dy/dx Weight, Xl-xg EXAMPLE 2 To the reaction vessel of Example 1 there is added 2280 parts of topped heptane, 5.25 parts diethylalurninum chloride and 8.31 parts titanium tetrachloride. The mixture is aged for approximately 1 hour at about 30 C. and there is commenced addition of ethylene at a rate of approximately pounds per hour. The reaction is carried on with stirring for approximately 52/3 hours at the end of which time the polymer slurry is withdrawn. There is separated therefrom polyethylene of an average molecular Weight of 39,000. Analysis of -this material as described in Example 1 yields the data for the integral and differential molecular weight distribution curves set forth respectively in Tables 3 and 4 which are plotted as FIG- URES 4 and 2 respectively.

Table 3 Toluene-n- Percentage C urnulative Molecular Frechen butanol, polymer percentage weight,1

volume based on polymer Mn ratio total 1 1.141X10a M uM.

Table 4 Molecular y1 yz dy weight dx dy/dx 14 17. 5 3 10-15, 000 5, 000 6.0 8.0 45.0 37 15-20. 000 5, 000 74. 0 48, 0 55. 0 7 20-25, 000 5, 000 14. 0 54. 5 57. 0 2, 5 25-30, 000 5, O00 5.0 56. 0 59.0 3.0 30-35, 090 5, 000 6.0 58, 5 66.0 7. 5 35-40, 000 5, 000 15.0 67.0 77. 0 10.0 40-45, 000 5,000 20.0 77.0 86. 5 9. 5 45-50, 000 5, 000 19. 0 88.0 95. 5 7. 5 50-55, 000 5, 000 15.0 95.5 98. 5 3. 0 55430, 000 5, 000 6.0 98. 5 100.0 1. 5 60-65, 000 5, 000 3.0 99. 5 100+ 1. 0 65-70, 000 5, O00 2. O

' The various catalysts falling within the general des`cription above can be substituted for the diethylaluminum chloride and titanium tetrachloride mixture utilized in Examples 1 and 2 to obtain results substantially identical thereto. It will be realized that variation of the amount of catalyst or of the molar ratio of catalyst component (A) and catalyst component (B) affects the molecular weight of the polyethylene produced. Preferably these catalysts are utilized in amounts of about 5-15 millimols each constituent per liter solvent. Generally the molar ratios can be varied -in the range of 0.5 :l to 12:1. Preferably, for the purposes of the present invention the molar ratios are varied in the range of from about 0.7511 to 2:1. Further, mixtures of titanium tetrachloride and diiso-butylduminum hydride, triethylaluminum, tributylaluminum and trioctylaluminum give superior results. Titanium oxychloride and titanium acetylacetonate, when substituted for titanium tetrachloride give excellent results.

As the inert solvent in the reaction zone is in the liquid form, when utilizing solvents normally gaseous at reaction temperatures such as pentane the system is operated under superatmospheric pressure. It will be realized that variation of the pressure in such instances can affect the boiling point of the inert solvent and thus the maximum temperature at which the system can operate at a given pressure. The advantages of operating the system under conditions at which the inert solvent is at its boiling point are described and claimed in the copending application of George W. Hooker and George O. Napack, Serial No. 513,576, Atiled concurrently herewith (now abandoned).

There can be substituted for the heptane utilized in Examples 1 and 2 the various inert solvents mentioned above to yield substantially similar results.

While the invention has been described with reference to particular embodiments thereof, it will be understood that in its broadest aspects the invention may be variously embodied within the scope of the invention as set iorth herein and in the appended claims.

I claim:

l. In a llow pressure, low temperature process for the polymerization of ethylene by contacting ethylene and a catalyst in the presence of an organic solvent at a temperature of from about 50 C. to about 100 C. and at a pressure below 100 atmospheres, in which the catalyst is a mixture of (A) and (B), component (A) being selected from the group consisting of an `alkyl aluminum, an alkyl aluminum chloride, and an `alkyl aluminum hydride and component I(B) being selected from the group consisting of titanium tetrachloride, titanium oxychloride, and titanium acetylacetonate, the molar ratio of component (A) to component (B) being in the range of 0.5 :1 to 12:1, the improvement in said low pressure, low temperature polymerization process which comprises continuously Iand simultaneously adding to a polymerization reaction zone ethylene and a mixture in an organic 6 solvent of said catalyst components (A) and (B) in a molar ratio of from 0.5:1 to 12:1, continuously polymerizing ethylene in said zone `at a temperature of from about 50 C. to about 85 C., continuously withdrawing 5 a polymer slurry from said zone at a rate to maintain the quantity of substituents in said reaction zone substantially constant, continuously separating said polymer slurry into a solid polyethylene phase and a liquid residue and returning the liquid residue to the polymerization 1() reaction zone.

2. A process of claim 1 in which the -inert hydrocarbon is heptane.

3. A process of claim 1 in which the inert hydrocarbon is hexane.

15 4. A process of claim 1 in which the inert hydrocarbon is pentane.

5. A process of claim 1 in which the inert hydrocarbon is xylene.

6. A process of claim 1 in which the inert hydrocarbon is propane.

7. A process of claim 1 in which catalyst component (A) is diethylaluminum chloride, and catalyst component (B) is titanium tetrachloride.

8. A process of claim 1 in which catalyst component (A) is triethyl aluminum and component (B) is titanium tetrachloride.

9. A process of claim 1 in which catalyst component (A) is triisobutylaluminum and catalyst component (B) is titanium tetrachloride.

10. A process of claim 1 in which catalyst component (A) Vis di-iso-butylaluminum hydride and catalyst component (B) is titanium tetrachloride.

v1l. A continuous low temperature, low pressure process for the production of polyethylene of uniform molecular Weight polymers which comprises polymerizing ethylene by continuously introducing ethylene, an organic solvent land a catalyst consisting essentially of a mixture of titanium tetrachloride vand diethyl aluminum hal-ide into a reaction zone, the mol ratio of diethyl aluminum halide to titanium tetrachloride being 0.3:1 to 4:1, at a temperature of 50 to 93 C., under about l1 to 6 atmosplie-res pressure, continuously withdrawing a polymer slurry from the reaction zone, and recovering the aforesaid uniform molecular weight polymers of polyethylene from said slurry.

References Cited in the le of this patent UNITED STATES PATENTS 2,425,638 Peterson Aug. 12, 1947 2,511,480 Roedel June `13, 1950 2,721,189 Anderson Oct. 18, 1955 FOREIGN PATENTS 533,362 Belgium May 16, 1955 

1. IN A LOW PRESSURE, LOW TEMPERATURE PROCESS FOR THE POLYMERIZATION OF ETHYLENE BY CONTACTIG ETHYLENE AND A CATALYST IN THE PRESENCE OF AN ORGANIC OLSVENT AT A TEMPERATURE OF FROM ABOUT 50*C. TO ABOUT 100*C. AND AT A PRESSURE BELOW 100 ATOMOSPHERES, IN WHCIH THE CATALYST IS A MIXTURE OF (A) AND (B), COMPONENT (A) BEING SELECTED FROM THE GROUP CONSISTING OF ALN ALKYL ALUMINUM, AN ALKYL ALUMINUM CHLORIDE, AND AN ALKYL ALUMINUM HYDRIDE AND COMPONENT (B) BEING SELECTED FROM THE GROUP CONSISTING OF TITANIUM THTRACHLORIDE, TITANIUM OXYCHLOFIDE, AND TITANIUM ACETHYLACETONATE, THE MOLAR RATIO OF COMPONENT (A) TO COMPONENT (B) BEING IN THE RANGE OF 0.5:1 TO 12:1, THE IMPROVEMENT IN SAID LOW PRESSURE, LOW TEMPERATURE POLYMERIZATION PROCESS WHICH COMPRISES CONTINUOUSLY AND SIMULTANEOUSLY ADDING TO A POLYMERIZATION REACTION ZONE ETHYLENE AND A MIXTURE IN AN ORGANIC SOLVENT OF SAID CATALYST COMPONENTS (A) AND (B) IN A MOLAR RATIO OF FROM 0.5:1 TO 12D1, CONTINUOUSLY POLYMERIZING ETHYLENE IN SAID ZONE AT A TEMPERATURE OF FROM ABOUT 50*C. TO ABOUT 85*C., CONTINUOUSLY WITHDRAWING A POLYMER SLURRY FROM SAID ZONE AT A RATE TO MAINTAIN THE QUANTITY OF SUBSTITUENTS IN SAID REACTION ZONE SUBSTANTIALLY CONSTANT, CONTINUOSLY SEPARATING SAID POLYMER SLURRY INTO A SOLID POLYETHYLENE PHASE AND A LIQUID RESIDUE AND RETURNING THE LIQUID RESIDUE TO THE POLYMERIZATION REACTION ZONE. 